Functionalized electrospun nanofibers for high efficiency removal of particulate matter

In recent years, introducing electrospun airfilters to enhance the removal of PM2.5 and PM10–2.5 has received much interest. In this study, a novel poly-(vinyl) alcohol (PVA)/carbon nanoparticle (CNP)/tea leaf extract (TLE), functionalized nanofibrous air filter (FNA) was fabricated using an electrospinning method. Novelty of the unique work in the blending of CNP and TLE, first of its kind, for the preparation of FNA. Polysaccharide crosslinked FNA has a carbon complex with two monosaccharide units to produce the intrinsic properties of the PM2.5 and PM10–2.5 removal efficiency. The FNA had promising traits of UV protection. The prepared FNA was characterized using physicochemical, mechanical, antimicrobial activity, etc., in addition to its PM2.5 and PM10–2.5 removal efficiency. Pore size and distribution study using the capillary flow porometry method has proved the structure of FNA. FNA exhibited excellent low pressure drop (110 Pa), which are promising characteristics for air purification. FNA from PVA: CNP: TLE exhibited high PM2.5 and PM10–2.5 removal efficiencies of 99.25% and 99.29%, respectively. Hence, the study proved.

Electrospinning is a unique technique for manufacturing nanostructured fibers with diameters ranging from the micro to the nano level. Polymeric-based electrospun materials with an average particle size of nanometers are extensively employed for airfilter applications. The materials are biocompatible, washable, reusable and low in weight. Micro and nanotechnology have benefited society in a variety of ways during the last few decades 1 . Nanofiber materials have attracted public attention due to their excellent surface fraction volume and prospective application in air filtration 2 .
Hazardous particulate matter (HPM) pollutants, which include particles, heavy metal dusts, toxic gases, spores, bacteria and organic pollutants including aerosol particles, benzene and polycyclic aromatic hydrocarbons are found in the atmosphere 3 . Small particles with a diameter of less than 2.5 µm in particular, run the risk of impairing human lung breathing and inhaling these particles raises the risk of teratogenic, carcinogenic and mutagenic effects as well as lung disorders such asthma, heart disease, stroke and lung cancer 4 . Effective protection of skin from exposure to sunlight needs a protective barrier so as to absorb or reflect the UV radiation before it reaches the skin surface 5 . Since, the attempt have been made to improve airfilters in order to improve their UV radiation protection efficiency. Particular matter 2.5 pollution particles in the air are made up of organic material such as elemental carbon and organic carbon, as well as inorganic matter such as SO 2 4 , NO 3 and SiO 2 . Hazardous air pollution arises from a range of sources including biomass burning, industrial emissions, soil dust, aerosols and coal combustion 6 . The behaviour of PM particles is influenced by chemical compositions, morphologies and mechanical qualities 7 . The Capture of various air pollutants, an effective electrospun air filter is a preferable option. The effectiveness of an air filter is determined by the type of air pollution and the pollutant capture mechanism can be adjusted 8 . Electrospun based ultralow particulate air filters and high-efficiency particulate air filters capture small particulate matter with filtration effectiveness of 98.99 (%) and 98.98 (%), respectively 9 . The metal adsorption process is classified as chemisorption or physisorption. Electrostatic attraction can also produce. The interaction of phenolic compounds with the activated carbon surface occurred in a monolayer adsorption type, limited by their more metal adsorption abilities 10 .

Synthesis of carbon nanoparticles (CNPs).
Olive oil was placed in 100 mL of earthenware pot and cotton wick was used to ignite the fire, which resulted in powder being emitted from the smoke. The powder was collected from the bottom of the earthenware pot using a standardized blade after 5 h and 10 g of the obtained powder was suspended in 200 mL of nitric acid in a 500 mL round bottom flask for refluxing for 28 h. The yellow supernatant was transferred to a conical flask and excess nitric acid was removed from the supernatant using a 3:2 ratio of acetone with water. The contents were then centrifuged at 12,000 rpm for 30 min to extract CNPs, which were then stored for further use 17 .

Extraction of tea leaf extract (TLE).
A normal hot water extraction process was used to extract the green tea leaves. One hundred milliliters of sterile boiling water was heated to 100 °C and the tea leaves were immersed in it and allowed to seep for 5 min. The TLEs were removed after 5 min and the extract was kept for further use. The green tea leaf extract was centrifuged at 5000 rpm for 5 min. TLE from microsized green tea extract brown colour particles was subjected to FTIR, SEM & EDX.
Fabrication of nanofibrous airfilter. PVA (8 w/w %) was dissolved in deionized water at room temperature. CNPs of 0.1% and TLE of 1 mL were added to the PVA solution and agitated at 80 °C until an electrospinning homogeneous solution was obtained. To obtain nanofibers, the electrospinning solution used a laboratory electrospinning machine 18 . A DC power supply (Spellman SL150), a syringe pump (NE1000 New Era Pump Systems, Inc) and a metal surfaced drum collector make up the installation. The electrospinning settings were 22 kV applied voltage at 0.15 mL/h flow rate and a needle (23 gauge) tip to drum distance of 20 cm. Finally, the nanofiber peal was obtained from the depositor collector. All experiments were conducted at room temperature. Two other nanofibrous airfilters were electrospun as PVA and PVA: CNPs.
Functionalization of nanofibrous airfilter (FNA). Nanofibrous mat specimens measuring 8.0 cm in length, 8.0 cm in width and 0.5 mm in thickness were examined prior to the stabilization process. The prepared cut samples were placed in a muffle furnace, preheated to 280 °C with a heating rate of 1 K/min, and then isothermally treated for 1 h at this temperature. These samples were provided a typical stabilization temperature of 600 °C for 1 h in a muffle furnace, and then allowed to cool before use. Ultraviolet protective test. UV-Vis spectroscopy was used to assess UV absorption. In one cuboid, the sample is inserted and the reference solvent is placed in the other cuboid. After interacting with UV-Vis light at room temperature, the sample spectra were obtained. All of the tests used a wavelength range of 250-800 nm.
Antimicrobial test. FNA was evaluated for antimicrobial performance against Staphylococcus aureus CECT240 (ATCC 6538p) and Escherichia coli ECT434 (ATCC 25922) strains procured from the Turkish type culture collection. Bacterial cultures were subcultured on nutrient agar medium and kept at room temperature (30 ± 2 °C). The antimicrobial performance of FNA was assessed using Ul-Islam et al. 19 . The inoculated samples were placed in bottles and incubated for 24 h at 24 °C with the pH of the agar media for microbial culture kept at 7.0 and the relative humidity at 95%. PVA, PVA: CNPs and PVA: CNPs: TLE samples with a size of 1 × 1 cm were prepared and subjected to the disc diffusion method. After 2 h of UV sterilization, the samples were placed on E. coli and S. aureus plates. The plates were incubated for 24 h at 37 °C. The diameter of the zone of inhibition against the organism was used to assess antibacterial efficacy.
Particulate matter (PM 2.5 & PM 10-2.5 ) efficiency of FNA. The PM removal efficiencies of PVA, PVA: CNPs and PVA: CNPs: TLE were determined in a small scale desigator setup to measure the effect of particle loading on the PM 2.5 and PM 10-2.5 removal efficiency of FNA. The experimental setup for assessing the PM 2.5 & PM 10-2.5 removal effectiveness as a function is shown in Fig. 1. The efficacy test setup was made of glass plates with dimensions of 750 mm × 60 mm × 60 mm (length × width × height). The middle of the layer was sealed with FNA with dimensions of 60 mm × 60 mm. Air pollution of cigarette smoke was employed to deliver air across the filter and PM 2.5 and PM 10-2.5 monitors were tested. Air quality measurements (Testo, 0563 4405, USA) were mounted at the smoking interior and outdoor setup to measure the air quality readings. The temperature and relative humidity in the lab were kept at 25 °C and 60%, respectively, during the experiments.

Statistical analysis.
The results are presented as the mean ± standard deviation (SD) for three individual experiments (n = 3). ANOVA (analysis of variance) and Duncan's multiple range analysis were performed to determine the significant differences among the different groups. P values of < 0.05 were considered significant.

Results and discussion
The FNA preparation is depicted in the schematic diagram (Fig. 1).

Characterization of CNPs and TLE.
The nanostructural morphology of CNPs and TLE were SEM images illustrated in Fig. 2a and b. CNP spherical particles ranged in size from 20 to 100 nm in diameter with an average particle size of approximately 60 nm. EDX spectrum of CNPs which indicated the presence of pure carbon. The morphology of TLE was smooth and distinct shapes were observed. The EDX spectrum of TLE was found to be free of any contaminants. The FTIR spectra of CNPs (Fig. 2c)     TGA . Figure 3a and b shows the TGA curves of PVA, PVA: CNPs and PVA: CNPs: TLE electrospun nanofibrous airfilter. The first stage was weight reduction to remove hydrogen bound water molecules from the polyphenolic structure at temperatures ranging from 100 to 200 °C. The second mass loss that occurred between 200 and 350 °C is linked to the backbone disintegration of PVA and TLE. PVA alone decomposes of side chain breaking at approximately 290 °C. The breakdown of CNPs causes the greatest weight loss in the temperature range of 320 to 480 °C. The OH and COOH groups in the polymeric chains allow the CNPs to interact with TLE and PVA. These interactions might result in the formation of weak intermolecular cross-links between polymeric chains 23 . Thermal deterioration of mineral byproducts causes the final stage which occurs at temperatures exceeding 500 °C.
SEM. Figure 4 shows Mechanical properties. Mechanical characteristics of airfilter membrane play a important role in determining their end use application perspectives. Mechanical characteristics such as tensile strength, elongation at break, flexing index, water absorption and water desorption were investigated ( Table 1). The results reveal that the mechanical properties of PVA: CNPs: TLE were higher than those of the other two samples 24 . This enhanced strength may be due to the impregnation of CNPs and TLE in PVA. Support of CNPs has enhanced the mechanical properties of the airfilter membrane, because these nanoparticles provide reinforcement effect with a combination of tensile strength and flexibility. Roohani-Esfahani et al. 25 reported that the dispersion microstructure of CNPs play a major role in the reinforcement of electrospun scaffold. The network structure and the inter- Water absorption and desorption play an important role in scaffold properties and their dimensional stability. Water absorption and desorption significantly (p < 0.05) increased in PVA: CNPs: TLE compared to the other two samples. These enhanced water absorption properties of electrospun scaffold could be attributed to the tea leaf extract and the formation of hydrogen bond between TLE and PVA 26 . Most of all leaf extract are hydrophilic in nature with a moisture content of 6-10% due to the presence of cellulose in cell membrane 27 . Water absorption and desorption capacity of a electrospun membrane play a considerable role in choosing its use in airfilter. Since, maintaining a dry product surface is essential to prevent moisture content and microbial growth. The durability test of FNA is given in Fig. 5. The stress-strain results reveal that FNA (after 10 h) had higher durability than the other h.  Fig. 6b. The pore size distribution of PVA: CNPs: TLE is mainly determined by the morphology and size of the nanofibers. 5.24 m 2 /g surface area, 0.15 cm 3 /g total pore volume and 76.90 nm average pore width was observed in PVA: CNPs: TLE. The surface to volume area, narrow distribution and small pore size, as well as the significantly high porosity, enable electrospun membranes to efficiently separate contaminants in air treatment 28 . The results demonstrate that PVA: CNPs: TLE had better pore size compared to PVA and PVA: CNPs.
Antimicrobial activity. The antimicrobial properties of PVA, PVA: CNPs and PVA: CNPs: TLE were tested following the disc diffusion method against E. coli and S. aureus. The results obtained from this clearly mention the inhibition zone of PVA, PVA: CNPs and PVA: CNPs: TLE (Fig. 7a,b). A shown in Table 2, PVA: CNPs: TLE had exhibited antimicrobial activity against the E.coli and S. aureus. Brady-Estevez 29 have reported that membrane airfilter form containing carbon nanoparticles played an important role in enhancing the antimicrobial activity against gram (−) and gram (+) bacteria. Microbial growth can be suppressed by the entry of CNPs into the cell membrane and also hindered by the formation of reactive oxygen species 30 . The antibacterial activity of tea leaf extract is attributed to polyphenols, which are two benzene rings as Aand Band pyridine derivatives are well characterized 31 . The physical interaction between the microbial membrane and fullerenes, in which CNPs cause DNA fragmentation in the cell membrane due to the particles' high surface hydrophobicity 32 .
Ultraviolet protective test. Figure 8 shows the UV spectra of PVA, PVA: CNPs and PVA: CNPs: TLE with nanofiber diameters of 175, 98 and 95 nm. According to the results, as the nanofiber diameter decreases from 175 to 95 nm. The UV-production performance of electrospun PVA: CNPs: TLE nanofibrous mats was determined by the nanofiber diameter according to our research observations. Smaller pore sizes have been demonstrated to produce better UV-production characteristics because they absorb UV radiation more effective 33 .    10-2.5 ) efficiency of FNA. Figure 9a depicts the test equipment used in this study to remove PM particles from the chamber which includes an our FNA (PVA, PVA: CNPs and PVA: CNPs: TLE). Figure 9b and c shows the PVA: CNPs: TLE, PM 2.5 removal efficiency of 99.21% and PM 10-2.5 efficiency of 99.28%. PVA: CNPs showed PM 2.5 and PM 10-2.5 removal efficiencies of 95.31% and 98.34%, respectively. PVA had a PM 2.5 removal efficiency of 90.23% and 91.45% PM 10-2.5 removal efficiency. Hence, PVA: CNPs: TLE had the best performance as a smoke airfilter. The filter particle counter and removal efficiency give a PM 2.5 and PM 10-2.5 calculated results according to a previous study in the literature 34 .
The PM capture process and demonstration are shown in Fig. 9d. PM particles captured by the nanofibers were bound tightly on the surface. In the case of PM, numerous mechanisms, such as diffusion, interception, inertia and gravity, work together to capture these particles 35 . The air filtration process was dominated by interception for particles with a diameter higher than the pore size of the filters. Gravity plays a crucial role in particle capture with the airflow perpendicular to the ground 36 . On the outside of PM particles, there are many functional groups with high polarity such as C-O, -SO 3 H, C-N and -NO 3 . As a result, functional groups as well as materials   Fig. 10a-c. As a result, the removal effectiveness of PM 2.5 and PM 10-2.5 was significantly improved as PM particles firmly wrapped around the nanofibers. The size distribution of smoke PM particles ranges from 400 nm, with the majority of particles being 1 mm. By decreasing the fiber diameter in the range of 100 to 200 nm, the PM 2.5 capture efficiencies increased. The fibrous structure of the electrospun scaffold and spherical shape were clearly observed in the results. Figure 10d shows the airfilter operation and tight binding of PM particles to produce an outstanding capture performance of the electrospun scaffold which was validated by microscopy. These results showed that the fiber diameter of PVA: CNPs: TLE was less than 150 nm, indicating that it has the ability to capture PM 2.5 and PM 10-2.5 . Figure 10e shows the elemental analysis of the prepared PVA: CNPs: TLE using EDX. Nanofiber diameters ranging from 60 to 200 nm have been found to improve particle capture of air molecules in previous studies 38 . In general, the pore size of a nanofiber filter has a weak relation with the PM 2.5 removal efficiency 39 . Nanofibers have proven to be useful in airfilters because of their small diameter and high surface to volume ratio, which improve particle absorption by interception 40 .
Elemental mapping (Fig. 11a-d) was performed on PVA: CNPs: TLE after exposure to PM 2.5 and the PM 10-2.5 removal effect. The surface of the nanofiber was successfully found by the uniform distribution of the elements. The EDX spectra of PM 2.5 and PM 10-2.5 removal by PVA: CNPs: TLE are shown in Fig. 11e. Carbon, oxygen and nitrogen element mapping seen on the nanofiber surface.
XPS. The presence of CNPs and TLE in PVA electrospun nanofibers was confirmed using surface chemistry scan spectra. The characterization of PM using X-ray photoelectron spectroscopy (XPS) is shown in Fig. 12. The XPS spectrum shows that the C1 s signal comprises three significant peaks at 284.7, 285.9 and 286.6 eV, which correspond to C-C, C-O and C=O bonds. The O1 s peaks showed the presence of C-O and C=O at 533.1 and 531.9 eV, respectively. In addition, a minor amount of N1 s was present on the surface of smoke particles, which was shown at the peak of 400.8 eV. The overall results was confirmed that C, O and N are three elements on the contaminated air PM surface and that the PM surface contained 58.5% carbon, 36.1% oxygen and 5.4% nitrogen, respectively. Chong et al. 41 reported that three elements had PM 2.5 capture surfaces.
In this research, PM was created by smoke burning. Exhaust smoke polluting gases such as SO2, NO2, CO2, CO and volatile organic compounds including polycyclic aromatic hydrocarbons, xylenes, benzene, toluene and aldehydes contain 40 mg g −133 . Electrospun nanofibrous membranes capture dust particles on their surfaces, which can be easily removed by back flushing or other mechanical methods 42 . In summary, the results of airfilter efficiency analysis suggested that the PVA: CNPs: TLE nanoairfilter promoted the process of PM 2.5 and PM 2.5-10 capture, indicating their great potential as airfilter applications.

Conclusion
In this research, we designed and developed electrospun FNA for PM 2.5 and PM 2.5-10 particle capture materials. Electrospun FNA exhibited physicochemical, mechanical and antimicrobial activity. An efficiency test demonstrated that particulate matter (PM 2.5 & PM 10-2,5 ) capture was significantly PM removed by these polluted air samples. All results show that these PVA: CNPs: TLE nanofilters have excellent PM filtration properties compared to PVA: CNPs and PVA filters. The prepared air filter was able to efficiently remove PM 2.5 and PM 2.5-10 from polluted air thus proving to be a viable and cost-effective strategy. In summary, these unique PVA: CNP: TLE nanofilters can be widely used in commercial, domestic and industrial places.